CN105658714B - Decorate film - Google Patents
Decorate film Download PDFInfo
- Publication number
- CN105658714B CN105658714B CN201480057954.4A CN201480057954A CN105658714B CN 105658714 B CN105658714 B CN 105658714B CN 201480057954 A CN201480057954 A CN 201480057954A CN 105658714 B CN105658714 B CN 105658714B
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- CN
- China
- Prior art keywords
- silver
- alloy
- silver alloy
- particulate
- decoration film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 129
- 238000005034 decoration Methods 0.000 claims abstract description 114
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 claims abstract description 40
- 239000004332 silver Substances 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009434 installation Methods 0.000 claims abstract description 22
- 239000004840 adhesive resin Substances 0.000 claims abstract description 21
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- 230000000052 comparative effect Effects 0.000 description 52
- 229910045601 alloy Inorganic materials 0.000 description 31
- 239000000956 alloy Substances 0.000 description 31
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 27
- 238000010586 diagram Methods 0.000 description 25
- 230000008859 change Effects 0.000 description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 21
- 235000013339 cereals Nutrition 0.000 description 18
- 230000004075 alteration Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910001961 silver nitrate Inorganic materials 0.000 description 11
- 238000002845 discoloration Methods 0.000 description 10
- 238000002310 reflectometry Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000010956 nickel silver Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 2
- 238000007811 spectroscopic assay Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical class CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/005—Manufacturers' emblems, name plates, bonnet ornaments, mascots or the like; Mounting means therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
- G01S13/00—Systems using the reflection or reradiation of radio waves, e.g. radar systems; Analogous systems using reflection or reradiation of waves whose nature or wavelength is irrelevant or unspecified
- G01S13/88—Radar or analogous systems specially adapted for specific applications
- G01S13/93—Radar or analogous systems specially adapted for specific applications for anti-collision purposes
- G01S13/931—Radar or analogous systems specially adapted for specific applications for anti-collision purposes of land vehicles
- G01S2013/9327—Sensor installation details
- G01S2013/93271—Sensor installation details in the front of the vehicles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
- G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
- G01S7/02—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S13/00
- G01S7/03—Details of HF subsystems specially adapted therefor, e.g. common to transmitter and receiver
- G01S7/032—Constructional details for solid-state radar subsystems
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Radar Systems Or Details Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The decoration film (10) formed on the surface of resin base (20) on the electromagnetism wave path positioned at radar installations, the decoration film (10) include：The silver alloy particulate (1a) being dispersed in the decoration film；With the light-transmissive adhesive resin (1b) for bonding silver alloy particulate (1a), wherein the silver alloy is made of the alloy of silver and zinc, the content of zinc is 0.5 to 50 quality % of silver.
Description
Background of invention
1. invention field
The present invention relates to the decoration films formed on the surface of resin base, relate more specifically to the excellent dress of anti-discoloration
Adorn film.
2. description of Related Art
Some vehicles, including motor vehicle are respectively equipped with the radar installations mounted on its front central, such as millimetre-wave radar,
To measure the vehicle and the distance between any barrier or vehicle existing for front.Radar installations passes through preceding grid and vehicle system
The radio wave that quotient's logo emits forward is made, such as millimeter wave is reflected by the object of the vehicle front, such as vehicle or barrier, and
Back wave passes through preceding grid etc. to return to radar installations.
Therefore, the material that reduces and can provide required attractive appearance is lost in radio wave transmissions and coating is usually used in
Positioned at the element or component in the beampath of radar installations, such as preceding grid and logo.In general, in the table of resin base
Decoration film is formed on face.
Meanwhile silver-colored film has been used for various uses because the film have high visible transmission than with excellent infrared ray
Shield property.Further, since silver-colored film also has excellent radio wave shield property, which can for example protect may be because
The electronic equipment of radio wave failure is from external radio wave action or electronic equipment can be inhibited to emit radio wave.Therefore
In the presence of using the case where silver-colored film is as radio wave shield film.
For example, Japanese patent application disclose No.2004-263290 (JP 2004-263290A) disclose containing 0.01 to
The silver alloy film for shielding radio wave of 10at% bismuths (Bi) and/or antimony (Sb).Use the covering of transparent dielectric film this
Silver alloy film for shielding radio wave.The document is mentioned, such as pin hole or cut so that straight even if defect occurs for this film
It connects and exposes silver alloy film, be also less likely to occur silver-colored aggregation.
But when for example silver is applied in a manner of being coated with resin base with silver-colored film as shown in JP 2004-263290 A
It is added on the surface of the resin base (such as logo) in the beampath from radar installations and is inhaled with for example enhancing design
When gravitation, then the radio wave sent out from radar installations, as millimeter wave is not easy to penetrate wherein.In consideration of it, for example, setting
Find out using silver-colored particulate and for bonding the adhesive resin of these particulates to form decoration film on the surface of the substrate.
But in this case, even if these silver-colored particulates in the decoration film are not directly exposed in air, contain
There is the decoration film of silver-colored particulate that can also pass through discoloration at any time.Even if using comprising silver and being added to it in such decoration film
In Bi silver alloy particulate, can not fully inhibit the discoloration.
Summary of the invention
The present invention, which is provided, to be formed and is being use up on the surface of the resin base in the beampath of radar installations
Pipe can also be substantially prevented from the decoration film of discoloration containing silver alloy particulate.
The present inventor hardy carry out studying and consequently found that, surface plasmon resonance inhalation effects silver or common
The surface of the particulate of silver alloy, to cause the discoloration of decoration film.That is, as shown in figure 12a, use up irradiation silver or
When the particulate of silver alloy, which vibrates the free electron movement so that in the particulate under the action of luminous energy, thus polarization silver
Or the particulate of silver alloy.Therefore, as shown in Figure 12B, generated on the surface of silver or the particulate of silver alloy and be referred to as surface etc.
Thus the surface electromagnetic wave of gas ions excimer/polariton is improved silver-colored or silver alloy thin with absorbing the light with specific wavelength
The energy (surface plasmon resonance absorption) of grain.As a result, the component around the particulate of silver or silver alloy is received and is somebody's turn to do
The energy of raising is so that decoration film discoloration；This is new discovery.Even if the present inventor is result, it is believed that selection is being tended to cause this
Also it is important that the specific silver alloy that surface plasmon resonance absorbs less easily is caused under the particulate state of class RESONANCE ABSORPTION
's.
The first aspect of the present invention is related on the surface of the resin base in the beampath of radar installations
The decoration film of formation.The decoration film includes being dispersed in the silver alloy particulate decorated in film and for bonding
The light-transmissive adhesive resin of silver alloy particulate is stated, wherein the silver alloy includes the alloy of silver and zinc, the content of zinc is relative to silver
For 0.5 to 50 quality %.
The second aspect of the present invention is related to shape on the surface of the resin base on being placed in the electromagnetism wave path of radar installations
At decoration film.The decoration film includes the silver alloy particulate being dispersed in the decoration film and is closed for bonding the silver
The light-transmissive adhesive resin of golden particulate, wherein the silver alloy includes the alloy of silver and nickel, the content of nickel is 1 to 30 relative to silver
Quality %.
Since these decoration films have including at least the silver alloy particulate being dispersed in the decoration film and are used for
The structure of the light-transmissive adhesive resin of the silver alloy particulate is bonded, the decoration film keeps metallescent appearance and has nothing
Line radio wave propagation property (electrical insulation property).
According to first and second aspect, by meeting silver-kirsite of above-mentioned alloy ratio or meeting above-mentioned alloy ratio
The silver alloy particulate that silver-nickel alloy is constituted is more effective compared with the particulate of other silver alloy to inhibit decoration film discoloration.
In the case of the zinc for the amount for containing the 0.5 mass % less than silver according to the silver alloy of first aspect or according to the
In the case that the silver alloy of two aspects contains the nickel of the amount of the 1 mass % less than silver, since the silver-colored ratio in the silver alloy is too high,
The decoration film may change colour.
Meanwhile in the case where containing the zinc of amount for the 50 mass % for having more than silver according to the silver alloy of first aspect or in root
It, should as zinc or nickel content improve in the case of the nickel for containing the amount for having more than 30 silver-colored mass % according to the silver alloy of second aspect
Decorating the brightness of film reduces.
It can be with 2 to 200 nanometers of average grain diameter according to the silver alloy particulate of first and second aspect.In silver alloy particulate
In the case of the average grain diameter more than 200 nanometers, silver alloy particulate tends to cause irregular reflection.It has been found that by
In this irregular reflection, silver-colored gloss tends to reduce.Therefore, desirable ranging from most the 200 of the average grain diameter of the silver alloy
Nanometer.Meanwhile in the case where silver alloy particulate has the average grain diameter less than 2 nanometers, it is less susceptible to reflection and is incident on the decoration
Light on film.
Particularly, although the silver alloy particulate with nano-grade size is total due to being referred to as local surface plasma excimer
Shake absorption the phenomenon that and tend to absorb light, but can inhibit meet it is thin according to the silver alloy of the alloy ratio of first or second aspect
Grain absorbs luminous energy.Therefore, although using this size silver alloy particulate, can also inhibit the decoration film change colour.
It can be with 2 to 98 nanometers of crystallite diameter according to the silver alloy of first and second aspect.It is less than 2 in its crystallite diameter
In the case of nanometer, it is less susceptible to the light that reflection is incident on the decoration film.Meanwhile being more than 98 nanometers of feelings in its crystallite diameter
Under condition, radio wave (electromagnetic wave) is less susceptible to penetrate the decoration film.
The present inventor speculates that in the first aspect, the peripheral surface for the particulate being made of the alloy of silver and zinc is by with height
In the zinc oxide coating of the resistance (resistance) of adhesive resin (resinous substrates), thus inhibit adhesive resin (resin
Matrix) change and inhibition cause to change colour.Meanwhile the present inventor speculates, in second aspect, is made of the alloy of silver and nickel thin
Grain inhibits surface plasmon resonance absorption simultaneously therefore to inhibit, and resinous substrates change and inhibition causes to change colour.
According to the present invention, even if using silver alloy particulate, can also fully inhibit positioned at the wave beam from radar installations
The decoration film discoloration formed on the surface of resin base in path.
Brief description
Below with reference to the accompanying drawings the feature, advantage and technology and industrial significance of the exemplary implementation scheme of the present invention are described,
Wherein like numerals refer to similar component, and wherein：
Fig. 1 is the schematic diagram of the decoration film of a diagram embodiment according to the present invention；
Fig. 2 is the schematic diagram for the construction that film is decorated shown in schematic thinking 1；
Fig. 3 is to show the preceding grid (resin base) positioned at vehicle front, the logo on its surface and positioned at the tree
The schematic diagram of relationship between the radar installations of aliphatic radical bottom rear and car；
Fig. 4 is to show the preceding grid (resin base) positioned at vehicle front, the logo on its surface and positioned at the tree
The schematic diagram of relationship between the radar installations of aliphatic radical bottom rear and car；
Fig. 5 be show according to the alloy ratio (Zn/Ag) of zinc in the silver alloy of embodiment 1 to 4 and comparative example 1 and 2 with make
With the diagram of the relationship between the aberration Δ Ε of the decoration film of these formation；
Fig. 6 be show according to the alloy ratio (Zn/Ag) of zinc in the silver alloy of embodiment 1 to 6 and comparative example 1 to 3 with make
With the diagram of the relationship between the initial L* values (before weather resistance test) of the decoration film of these formation；
Fig. 7 be show the alloy ratio (Zn/Ag) in the zinc-silver alloy of embodiment 7 and the relationship between initial L* values and
The diagram of the relationship between alloy ratio (Bi/Ag) and initial L* values in the Bi- silver alloy of comparative example 4；
Fig. 8 be show using silver alloy particulate obtain according to embodiment 8 and 9 and comparative example 5 to 7 decoration film and color
The diagram of relationship between poor Δ Ε；
Fig. 9 be show be incident on using silver alloy particulate obtain according to embodiment 8 and 9 and comparative example 5 to 7 decoration apply
The diagram of relationship between the wavelength of light on film and the reflectivity for decorating film；
Figure 10 be show using silver alloy particulate obtain according to embodiment 10 to 13 and comparative example 8 and 9 decoration film
The diagram of relationship between aberration Δ Ε；
Figure 11 be show be incident on using silver alloy particulate obtain according on the decoration film of embodiment 10 and comparative example 8
Light wavelength and decorate film reflectivity between relationship diagram；
How Figure 12 A are diagram silver alloy particulates by one group of Light polarizing view；And
Figure 12 B are the views for illustrating surface plasmon resonance and absorbing.
Embodiment is described in detail
Fig. 1 is the schematic diagram of an embodiment of the decoration film of the diagram present invention.Fig. 2 is shown in schematic thinking 1
Decorate the schematic diagram of the construction of film.Fig. 3 is to show the preceding grid (resin base) positioned at vehicle front, be located at preceding grid surface
On logo and positioned at the resin base rear and car radar installations between relationship schematic diagram.Fig. 4 is that display is located at
The preceding grid (resin base) of vehicle front, the logo on preceding grid surface and positioned at the resin base rear and car
The schematic diagram of relationship between radar installations.
Film 10 is decorated shown in Fig. 1 constitutes the emblem that be mounted on the surface of resin base 20 (it is preceding grid)
Mark.As shown in Figure 3, the radar installations D in being mounted on before car body A is located at the rear of preceding grid.It is sent out from radar installations D
The millimeter wave (millimeter wave L1) gone out passes through preceding grid and the logo on its surface to emit forward as shown in Figure 4, and by vehicle
Object in front of, as vehicle or barrier reflect.Back wave (millimeter wave L2) passes through logo and preceding grid to return to radar installations
D.Decoration film (logo) is being formed on the surface for the resin base 20 being placed in radar installations beampath as a result,.
The table of the resin base 20 being placed in radar installations beampath (preceding grid) is applied to since film 10 will be decorated
On face, which keeps metallescent appearance and has radio propagation property (electrical insulation property).
Specifically, as shown in fig. 1, by being superimposed bright layers 1 and transparent along the direction (direction X) for watching decoration film 10
Resinous coat 2 and be integrally formed decoration film 10.Incidentally, can be wherein by stick in decoration film 10
(sticker) etc. it is applied in bright layers 1 and pastes the stick in resin base 20.As shown in Figure 2, bright layers 1 are at least wrapped
Include the silver alloy particulate 1a being dispersed in the decoration film and the light-transmissive adhesive resin 1b for bonding silver alloy particulate 1a.More
It is preferred that dispersant (protective agent) 1c is added further in bright layers 1 to improve the dispersibility of silver alloy particulate 1a.
In the bright layers 1 of decoration film 10, silver alloy particulate discontinuously disperses in this layer as described above, and due to the silver
Alloy is nano-particle, and particle is with interparticle apart from extremely short.The particle therefore fine and close aggregation.Therefore, which provides
The visible metallescent appearance of human eye, and radio wave penetrates nano-particle under extremely slight Attenuation.Therefore, the painting
Film can keep metallescent appearance and have electrical insulation property.
Incidentally, the term as used herein " millimeter wave " refers to the radio with about 30 to 300GHz frequency band
The millimeter wave with about 76GHz frequencies in wave, such as the frequency band.The term as used herein " decoration film " refers in composition
State the element of distinctive decorated articles feature of vehicular manufacturer's logo, vehicle etc..On the surface for the preceding grid of resin base
It is formed and constitutes or include logo etc. of the decoration film as its component part by this decoration film.
In this embodiment, the silver alloy for constituting silver alloy particulate 1a be the alloy of silver and zinc and containing silver 0.5 to
The zinc of the amount of 50 mass %.On the other hand, the silver alloy for constituting silver alloy particulate 1a be the alloy of silver and nickel and containing silver 1 to
The nickel of the amount of 30 mass %.
The experiment carried out from the present inventor being described later on is found out, as described above by meeting above-mentioned alloy ratio (Zn/Ag:
0.5 to 50 quality %) silver-kirsite or meet above-mentioned alloy ratio (Ni/Ag:1 to 30 quality %) silver-nickel alloy constitute
Silver alloy particulate more effective compared with the particulate of other silver alloy inhibit decoration film discoloration.
Contain 1 less than silver in the case of the zinc for the amount that silver alloy contains the 0.5 mass % less than silver or in silver alloy
In the case of the nickel of the amount of quality %, since the silver-colored ratio in the silver alloy is too high, which may change colour.
Meanwhile silver alloy contain have more than silver 50 mass % amount zinc in the case of or silver alloy contain have more than silver
In the case of the nickel of the amount of 30 mass %, the brightness of the decoration film reduces.
Here, the term " particulate " in the embodiment for silver alloy refers to " nano-particle ", and " nano-particle " is
Particle with nanoscale average grain diameter.The example for measuring the method for the grain size of nano-particle includes following methods：The wherein figure
As a certain in upper scanning electron microscope (SEM) image for extracting silver alloy particulate or transmission electron microscope (TEM) image
Metallic present in region, and measure the average grain diameter of the particle of extraction.
Particularly, although the silver alloy particulate with nano-grade size is total due to being referred to as local surface plasma excimer
Shake absorption the phenomenon that and tend to absorb light, but can inhibit the above-mentioned alloy ratio for meeting zinc or nickel silver alloy particulate absorb light
Energy.Therefore, although using size silver alloy particulate so, the decoration film can also be inhibited to change colour.
No matter the silver alloy is zinc-silver or nickel-silver alloy, which is preferably provided with 2 to 200 nanometers and is averaged
Grain size.In the case where silver alloy particulate has the average grain diameter more than 200 nanometers, silver alloy particulate tends to cause irregular
It reflects, thus silver-colored gloss tends to reduce.Meanwhile in the case where silver alloy particulate has the average grain diameter less than 2 nanometers, compared with
It is not easy the light that reflection is incident on the decoration film.
In addition, the silver alloy is preferably with 2 to 98 nanometers of crystallite diameter.The case where its crystallite diameter is less than 2 nanometers
Under, it is less susceptible to the light that reflection is incident on the decoration film.Meanwhile in the case where its crystallite diameter is more than 98 nanometers, wirelessly
Electric wave (electromagnetic wave) is less susceptible to penetrate the decoration film.
Can be for example by the way that reducing agent be added to solion --- wherein silver and respectively with silver formation alloy zinc or
Nickel is ionic state --- in manufacture such silver alloy particulate.The particulate obtained by this manufacturing method is nano-grade size
Particle.
Silver and zinc or the composition of the alloy of nickel can be adjusted by changing amount of metal contained in the solion.It is inciting somebody to action
Reducing agent introduces after the solion of silver and zinc or nickel ion, stirs this solution.By controlling stirring for solion
It mixes period and its heating temperature is used for by control, the crystallite of the average grain diameter and silver alloy that can adjust silver alloy particulate is straight
Diameter.
Resinous coat 2 and adhesive resin 1b are light penetrating copolymer resins.The example includes acrylic resin, makrolon
Resin, poly- (ethylene glycol terephthalate) resin, epoxy resin and polystyrene resin.
In the case where adding dispersant (protective agent) 1c, dispersant (protective agent) 1c preferably has and silver alloy particulate
The resin of the good adhesion of 1a and good affinity to adhesive resin 1b.Text is pointed out any as example in the choice
In the case of adhesive resin, wherein the resin for having been incorporated into carbonyl is preferred.For example, select acrylic resin as bonding
In the case of agent resin 1b, the acrylic resin with carbonyl is preferably selected as dispersant (protective agent) 1c.
Such dispersant (protective agent) with carbonyl can be with the bonding force with silver alloy particulate 1a of enhancing.In addition,
By selecting identical resin as adhesive resin 1b, the affinity to adhesive resin 1b can be enhanced.
The content of silver alloy particulate 1a preferably should be 83 to 99 quality % in entire bright layers 1.It is less than 83 matter in its content
In the case of measuring %, there is a situation where that the metallic luster for being attributed to silver alloy particulate 1a is insufficient.It is more than 99 mass % in its content
In the case of, there is the hypodynamic situation of the bonding with substrate for being attributed to adhesive resin 1b.
The present invention is explained referring to embodiment.
<Embodiment 1>220 grams of silver nitrates are mixed into the zinc ratio so that in manufactured silver alloy particulate with 3.84 grams of zinc nitrates
Example (alloy ratio：Percentage composition) relative to silver be 1 mass %.This mixture is added to the (reduction of 597 grams of amino alcohols
Agent) in, hereafter ingredient is heated and is mixed 120 minutes at 60 DEG C to precipitate silver alloy particulate.By gained mixture in room temperature
3 hours (50 nanometers of average grain diameters of particulate of lower ultrafiltration；10 nanometers of the crystallite diameter of silver alloy).
Then, by be used as ingredient mix 40 grams of dihydroxypropane single-ethers, 8.86 grams of styrene, 8.27 grams of acrylic acid ethyls oneself
Ester, 15 grams of lauryl methacrylates, 34.8 grams of 2-Hydroxyethyl methacrylate, 3.07 grams of methacrylic acids, 30 grams of sour phosphorus oxygens
The polymerization of six monomethacrylates of base (acid phosphoxyhexamonomethacrylate), 43 grams of dihydroxypropane single-ethers
Initiator and 0.3 gram of tert-butyl peroctoate, prepare mixture 1.By the mixture 1 of 0.465 gram of part and 0.38 gram of Disperbyk
190 (BYK Japan KK manufactures), 0.23 gram of Epocros WS-300 (NIPPON SHOKUBAI CO., LTD. manufacture), 0.09
Gram BYK-330 (BYK Japan KK manufactures) and 150 grams of 1- ethyoxyl -2- propyl alcohol are mixed to prepare coating.Using the coating as
Adhesive resin is mixed with silver alloy particulate.Then, as spin coating apply obtained by mixture and be heat-treated 30 minutes at 80 DEG C.
Decoration film is consequently formed.
<Embodiment 2 to 7>Decoration film is formed in the same manner as in example 1.Embodiment 2 to 7 and embodiment 1
Difference lies in change the mixing ratio of silver nitrate and zinc nitrate to generate alloy ratio shown in Fig. 5 or 6.
<Comparative example 1 to 3>Decoration film is formed in the same manner as in example 1.The area of comparative example 1 and embodiment 1
It is not to be added without zinc nitrate, and comparative example 2 and 3 is with it that difference lies in change the mixing ratio of silver nitrate and zinc nitrate to generate
Alloy ratio shown in Fig. 5 or 6.
[weather resistance test (xenon experiment)] according to the decoration film of embodiment 1 to 4 and comparative example 1 to 3 to imposing weather-proof examination
Test (xenon experiment) (100W x 125MJ/m2).Before and after weather resistance test, according to CIE1976 color systems (JIS
Z8729 the color system (L*, a*, b*) provided in), with color and colour difference meter (CMS-35sp, MURAKAMI COLOR
RESEARCH LABOLATORY, INC. manufacture) check the brightness L* of decoration film according to embodiment 1 to 4 and comparative example 1 to 3
With chromaticity index a* and b*.The aberration Δ Ε of each decoration film is calculated by these values.
Fig. 5 be show according to the alloy ratio (Zn/Ag) of zinc in the silver alloy of embodiment 1 to 4 and comparative example 1 and 2 with make
With the diagram of the relationship between the aberration Δ Ε of the decoration film of alloy formation.Fig. 6 is display according to embodiment 1 to 7 and right
In the silver alloy of ratio 1 to 3 alloy ratio (Zn/Ag) of zinc with using the alloy formed decoration film initial L* values (
Before weather resistance test) between relationship diagram.
(result 1) as shown in Figure 5, the aberration of the decoration film of embodiment 1 to 4 before and after weather resistance test is less than
The decoration film of comparative example 1 and 2.Containing less than relative to silver be 0.5 mass % amount zinc silver alloy in the case of (packet
The case where including without zinc), which changes colour (color change).
As shown in Figure 6, the initial L* values of the decoration film of embodiment 1 to 7 are higher than the decoration film of comparative example 3.As a result
Show that containing the alloy relative to the zinc for the amount that silver is 50 mass % is had more than, the brightness of the decoration film reduces.
<Embodiment 7>Decoration film is formed in the same manner as in example 1.Embodiment 7 and the difference of embodiment 1 exist
In the mixing ratio of change silver nitrate and zinc nitrate to generate alloy ratio shown in fig. 7.
<Comparative example 4>Decoration film is formed in the same manner as in example 1.Comparative example 4 and the difference of embodiment 1 exist
In replacing zinc nitrate using bismuth nitrate to generate the particulate that is constituted of alloy by silver and bismuth and change the mixed of silver nitrate and bismuth nitrate
Composition and division in a proportion is to generate alloy ratio shown in fig. 7.
[measurement of initial L* values] checks the decoration according to embodiment 7 and comparative example 4 in the same manner as in example 1
The initial L* values of film.Fig. 7 is to show the alloy ratio (Zn/Ag) in the zinc-silver alloy of embodiment 7 and between initial L* values
The diagram of the relationship between alloy ratio (Bi/Ag) and initial L* values in the Bi- silver alloy of relationship and comparative example 4.
(result 2) as shown in Figure 7, even if when improving alloy ratio embodiment 7 decoration film initial L* values
Hardly reduce.Meanwhile as alloy ratio improves, the initial L* values of the decoration film of comparative example 4 reduce and turn yellow.
<Embodiment 8>Form decoration film in the same manner as in Example 1.
<Embodiment 9>Decoration film is formed in the same manner as in example 1.Embodiment 9 and the difference of embodiment 1 exist
In replacing zinc nitrate using nickel nitrate, to generate the particulate being made of the alloy of silver and nickel, (it is 1 mass %'s to contain relative to silver
The particulate of the nickel of amount).
<Comparative example 5>It is formed and identical decoration film in comparative example 1.
<Comparative example 6 and 7>Decoration film is formed in a manner of in the same manner as in Example 8.The area of comparative example 6 and embodiment 8
It is not to replace zinc nitrate using bismuth nitrate to generate the particulate that is constituted of alloy by silver and bismuth, and the difference of comparative example 7 and its
It is to replace zinc nitrate using palladium nitrate to generate the particulate being made of the alloy of silver and palladium.
In the same manner as in example 1 to according to embodiment 8 and 9 and comparative example 5 to 7 decoration film impose it is weather-proof
Experiment (xenon experiment) simultaneously calculates its aberration Δ Ε.Fig. 8 be show using silver alloy particulate obtain according to embodiment 8 and 9 Hes
The diagram of relationship between the decoration film and aberration Δ Ε of comparative example 5 to 7.
[measurement of reflectivity] before weather resistance test, use up irradiation according to embodiment 8 and 9 and comparative example 5 to 7 decoration apply
Film.By reflectivity of the gained spectroscopic assay decoration film of these decoration films under each wavelength.Fig. 9 is that display is incident on use
Silver alloy particulate obtain according to embodiment 8 and 9 and comparative example 5 to 7 decoration film on light wavelength and decoration film
The diagram of relationship between reflectivity.
(result 3) as shown in Figure 8, there is the decoration film of embodiment 8 and embodiment 9 decoration than comparative example 5 to 7 to apply
The small aberration Δ Ε of film.As shown in Figure 9, compared with embodiment 8 and 9, the reflectivity bigger of the decoration film of comparative example 5 to 7
Ground becomes with wavelength.
(discussing 1) as shown in figure 9, compared with embodiment 8 and 9, the reflectivity of the decoration film of comparative example 5 to 7 is larger
Become with wavelength.This shows that, when using up irradiation according to the particulate of the silver of comparative example 5 to 7 or silver alloy, absorbing has certain wave
Long light component.The energy of the particulate of silver or silver alloy is considered thus improving (surface plasmon resonance absorption).According to
Think, therefore, as shown in Figure 8, the component around the particulate of silver or silver alloy receives the energy of the raising so that decoration
Film changes colour.Think simultaneously, in the case of embodiment 8 and 9 given above and embodiment 1 to 7, surface plasma excimer
RESONANCE ABSORPTION is suppressed, therefore is inhibited the component around alloy particulate to receive and continuously used up the energy that irradiation generates, by
This can prevent the decoration film from changing colour.Speculated by the further analysis of the present inventor, the particulate being made of the alloy of silver and zinc
Peripheral surface be coated with by the zinc oxide with the resistance (resistance) higher than adhesive resin (resinous substrates), and therefore
Adhesive resin (resinous substrates) change and inhibition is inhibited to cause to change colour.Speculate simultaneously, the particulate being made of the alloy of silver and nickel
Inhibit surface plasmon resonance to absorb and therefore inhibition adhesive resin (resinous substrates) changes and inhibition causes to change colour.
<Embodiment 10 to 14>Decoration film is formed in the same manner as in example 1.Embodiment 10 to 14 and implementation
Example 1 difference lies in use nickel nitrate to replace zinc nitrate with generate the particulate that is constituted of alloy by silver and nickel and change silver nitrate and
The mixing ratio of nickel nitrate is to generate alloy ratio shown in table 1 (percentage composition of Ni).
<Comparative example 8 to 11>Decoration film is formed in a manner of in the same manner as in Example 10.Comparative example 8 and embodiment 10
Difference lies in being added without nickel nitrate, and comparative example 9 to 11 with its difference lies in the mixing ratio for changing silver nitrate and nickel nitrate with
Generate alloy ratio shown in table 1.
It is resistance to being imposed according to the decoration film of embodiment 10 to 13 and comparative example 8 and 9 in the same manner as in example 1
It waits experiment (xenon experiment) and calculates its aberration Δ Ε.Figure 10 be show using silver alloy particulate obtain according to embodiment 10 to
The diagram of relationship between 13 and comparative example 8 and 9 decoration film and aberration Δ Ε.
Before weather resistance test, checked in the same manner as in example 1 according to embodiment 10 to 14 and comparative example 9 to 11
Decoration film initial L* values.Its result is shown in table 1.The visual inspection of metal luster (minute surface) is also shown in table 1.
Before weather resistance test, by using up irradiation according to embodiment 10 and right with identical method in above-mentioned measuring reflectance
The decoration film of ratio 8.By reflectivity of the gained spectroscopic assay decoration film of these decoration films under each wavelength.Figure 11 is
Display is incident on the wavelength and dress according to the light on the decoration film of embodiment 10 and comparative example 8 obtained using silver alloy particulate
Adorn the diagram of the relationship between the reflectivity of film.
[table 1]
(result 4) as shown in Figure 10, the aberration of the decoration film of embodiment 10 to 13 before and after weather resistance test
Less than the decoration film of comparative example 8 and 9.Containing less than relative to silver be 1.0 mass % amount nickel silver alloy the case where
Under (including not nickeliferous situation), decoration film discoloration.
Meanwhile as shown in table 1, the initial L* values of the decoration film of embodiment 10 to 14 are higher than the dress of comparative example 10 and 11
Adorn film.These results indicate that containing the silver alloy relative to the nickel for the amount that silver is 30 mass % is had more than, the dress
Adoring the brightness of film reduces.As shown in Figure 11, compared with Example 10, comparative example 8 decoration film reflectivity larger
Become with wavelength.
(discuss 2) it is thought that as shown in Figures 10 and 11, in the case of the particulate being made of the alloy of silver and nickel, table
The absorption of surface plasma plasmon resonance is suppressed, therefore the component reception around alloy particulate is inhibited continuously to use up irradiation
Energy (adhesive resin is inhibited to change) in the process, thus, it is possible to inhibit the decoration film to change colour.
<Embodiment 15>Decoration film is formed in the same manner as in example 1.The difference of embodiment 15 and embodiment 1
It is to change heating temperature when mixing silver nitrate, zinc nitrate and amino alcohol and for its incorporation time to produce
The raw silver alloy particulate with 200 nanometers in average diameter.Incidentally, the TEM image of silver alloy particulate is extracted on this image
In a certain region present in metallic, and measure the average grain diameter of the particle of extraction.
<Comparative example 12>Decoration film is formed in a manner of identical with embodiment 15.The area of comparative example 12 and embodiment 15
It is not to change the heating temperature of silver nitrate, zinc nitrate and amino alcohol and there are 500 nanometers to generate for its incorporation time
The silver alloy particulate of average grain diameter.
(result 5) checks the decoration film of embodiment 15 and comparative example 12, as a result, it has been found that, in film (its of comparative example 12
Middle silver alloy particulate has the average grain diameter more than 200 nanometers) in, silver alloy particulate causes irregular reflection and its silver-colored gloss inclines
To in the film less than embodiment 15.Also according to the crystallite diameter inspection result being described later on, which is preferably 2 nanometers
Or bigger.
<Embodiment 16>Decoration film is formed in the same manner as in example 1.The difference of embodiment 16 and embodiment 1
It is to change heating temperature when mixing silver nitrate, zinc nitrate and amino alcohol and for its incorporation time to produce
The raw silver alloy with 2 to 98 nanometers of crystallite diameter (specifically, 2 nanometers, 25 nanometers and 98 nanometers crystallite diameter).It is suitable
Just it refers to, the crystallite diameter of each silver alloy is measured by the X-ray diffraction method provided in such as JISH7805.
<Comparative example 13>Decoration film is formed in a manner of identical with embodiment 16.The area of comparative example 13 and embodiment 16
It is not to change the heating temperature of silver nitrate, zinc nitrate and amino alcohol and is received less than 2 for its incorporation time with generating to have
The silver alloy of rice or crystallite diameter (specifically, 1 nanometer and 99 nanometers crystallite diameter) more than 98 nanometers.
(result 6) checks the decoration film of embodiment 16 and comparative example 13, as a result, it has been found that, it is less than 2 nanometers in crystallite diameter
Comparative example 13 film in the case of, be less susceptible to the incident light on it of reflection.Meanwhile in crystallite diameter it being more than 98 nanometers
In the case of the film of comparative example 13, which is less susceptible to transmission radio wave (electromagnetic wave).The decoration of embodiment 16 applies
Film has metallic luster and satisfactory radio wave transmissions property.
Although embodiment of the present invention is described in detail by reference to attached drawing, concrete configuration is not limited to the embodiment party
Case.Any design modification in spirit of that invention or the like includes within the present invention.
Claims (5)
1. decorating film, formed on the surface of the resin base on being placed in the electromagnetism wave path of radar installations, the decoration
Film is characterized in that：
The silver alloy particulate being dispersed in the decoration film；With
Light-transmissive adhesive resin for bonding the silver alloy particulate,
The wherein described silver alloy is made of silver and the alloy of zinc substantially, and the content of zinc is 1 to 50 quality % relative to silver.
2. decorating film, formed on the surface of the resin base on being placed in the electromagnetism wave path of radar installations, the decoration
Film is characterized in that：
The silver alloy particulate being dispersed in the decoration film；With
Light-transmissive adhesive resin for bonding the silver alloy particulate,
The wherein described silver alloy is made of silver and the alloy of nickel substantially, and the content of nickel is 1 to 30 quality % relative to silver.
3. according to the decoration film of claims 1 or 2, wherein the silver alloy particulate has 2 to 200 nanometers of average grain diameter.
4. according to the decoration film of claims 1 or 2, wherein the silver alloy has 2 to 98 nanometers of crystallite diameter.
5. decoration film according to claim 3, wherein the silver alloy has 2 to 98 nanometers of crystallite diameter.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-221071 | 2013-10-24 | ||
| JP2013221071A JP5811157B2 (en) | 2013-10-24 | 2013-10-24 | Decorative coating |
| PCT/IB2014/002156 WO2015059539A1 (en) | 2013-10-24 | 2014-10-20 | Decorative coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105658714A CN105658714A (en) | 2016-06-08 |
| CN105658714B true CN105658714B (en) | 2018-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480057954.4A Active CN105658714B (en) | 2013-10-24 | 2014-10-20 | Decorate film |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20160256891A1 (en) |
| JP (1) | JP5811157B2 (en) |
| CN (1) | CN105658714B (en) |
| DE (1) | DE112014004880B4 (en) |
| WO (1) | WO2015059539A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017200383A1 (en) * | 2017-01-11 | 2018-07-12 | Astyx Gmbh | Radar sensor with two-dimensional beam tilting and L, U or T-shaped structure for installation in the front radiator area of the automobile |
| JP2018128341A (en) | 2017-02-08 | 2018-08-16 | トヨタ自動車株式会社 | Decorative coating |
| JP6930417B2 (en) | 2017-12-22 | 2021-09-01 | トヨタ自動車株式会社 | Decorative coating |
| DE112019002047T5 (en) | 2018-05-17 | 2021-01-07 | Ikuyo Co., Ltd. | DECORATIVE ELEMENT |
| CN113445034A (en) * | 2020-03-27 | 2021-09-28 | 丰田自动车株式会社 | Method for producing metal-like film and metal-like film |
| JP7343472B2 (en) * | 2020-12-25 | 2023-09-12 | トヨタ自動車株式会社 | Radio wave transparent cover and its manufacturing method |
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| CN1339614A (en) * | 2000-08-25 | 2002-03-13 | 斯特恩－利奇公司 | Anti-color changing hardenable pure silver alloy |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN102227646A (en) * | 2008-12-01 | 2011-10-26 | 丰田自动车株式会社 | Decorative film and method for decorative film formation |
| CN102232121A (en) * | 2010-09-08 | 2011-11-02 | 深圳市大凡珠宝首饰有限公司 | Anti-tarnish silver alloy and method for manufacturing the same |
| WO2012114180A2 (en) * | 2011-02-22 | 2012-08-30 | Toyota Jidosha Kabushiki Kaisha | Decorative coating |
| CN102906309A (en) * | 2010-04-22 | 2013-01-30 | 日本化药株式会社 | Silver anti-tarnishing agent, silver anti-tarnishing resin composition, silver anti-tarnishing method, and light-emitting diode using same |
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| JP3997177B2 (en) | 2002-08-09 | 2007-10-24 | 株式会社神戸製鋼所 | Ag alloy film for forming electromagnetic wave shield, Ag alloy film forming body for electromagnetic wave shield, and Ag alloy sputtering target for forming Ag alloy film for electromagnetic wave shield |
| GB0507049D0 (en) * | 2005-04-07 | 2005-05-11 | Univ Sheffield Hallam | Silvery alloy compositions |
| EP1889931A4 (en) * | 2005-06-10 | 2011-09-07 | Tanaka Precious Metal Ind | Silver alloy having excellent reflectivity/transmissivity maintaining characteristics |
| EP1889930A4 (en) * | 2005-06-10 | 2011-09-07 | Tanaka Precious Metal Ind | Silver alloy having excellent reflectivity/transmissivity maintaining characteristics |
| JP2009102626A (en) * | 2007-10-05 | 2009-05-14 | Nippon Sheet Glass Co Ltd | Electromagnetic wave permeable coated resin component for vehicle |
| JP5163715B2 (en) * | 2010-08-27 | 2013-03-13 | トヨタ自動車株式会社 | Electromagnetic wave transmissive coating film having glitter, electromagnetic wave transmissive coating composition for forming the same, and electromagnetic wave transmissive film forming method using the same |
-
2013
- 2013-10-24 JP JP2013221071A patent/JP5811157B2/en active Active
-
2014
- 2014-10-20 US US15/030,725 patent/US20160256891A1/en not_active Abandoned
- 2014-10-20 WO PCT/IB2014/002156 patent/WO2015059539A1/en active Application Filing
- 2014-10-20 DE DE112014004880.1T patent/DE112014004880B4/en active Active
- 2014-10-20 CN CN201480057954.4A patent/CN105658714B/en active Active
-
2019
- 2019-09-04 US US16/559,697 patent/US20200001323A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339614A (en) * | 2000-08-25 | 2002-03-13 | 斯特恩－利奇公司 | Anti-color changing hardenable pure silver alloy |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN102227646A (en) * | 2008-12-01 | 2011-10-26 | 丰田自动车株式会社 | Decorative film and method for decorative film formation |
| CN102906309A (en) * | 2010-04-22 | 2013-01-30 | 日本化药株式会社 | Silver anti-tarnishing agent, silver anti-tarnishing resin composition, silver anti-tarnishing method, and light-emitting diode using same |
| CN102232121A (en) * | 2010-09-08 | 2011-11-02 | 深圳市大凡珠宝首饰有限公司 | Anti-tarnish silver alloy and method for manufacturing the same |
| WO2012114180A2 (en) * | 2011-02-22 | 2012-08-30 | Toyota Jidosha Kabushiki Kaisha | Decorative coating |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200001323A1 (en) | 2020-01-02 |
| WO2015059539A1 (en) | 2015-04-30 |
| US20160256891A1 (en) | 2016-09-08 |
| DE112014004880B4 (en) | 2017-06-08 |
| JP2015080934A (en) | 2015-04-27 |
| DE112014004880T5 (en) | 2016-07-07 |
| JP5811157B2 (en) | 2015-11-11 |
| CN105658714A (en) | 2016-06-08 |
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